tris(tetramethylammonium) phosphate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: tris(tetramethylammonium) phosphate
• 英文别名: Tetramethylazanium;phosphate
• 化学式: 3C₄H₁₂N*O₄P
• 分子量: 317.409
• InChiKey: WOERBKLLTSWFBY-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  -2.5
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  86.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tris(tetramethylammonium) phosphate 在 basic anion exchanger 作用下， 以 水 为溶剂， 生成 四甲基氢氧化铵
  参考文献：
  名称：

  [DE] VERFAHREN ZUR HERSTELLUNG VON QUARTÄREN AMMONIUM-VERBINDUNGEN
  [EN] METHOD FOR PRODUCING QUATERNARY AMMONIUM COMPOUNDS
  [FR] PROCÉDÉ DE PRODUCTION DE COMPOSÉS D'AMMONIUM QUATERNAIRES

  摘要：

  本发明涉及一种制备季铵化合物的方法，其中将含有sp3杂化氮原子的化合物与二烷基硫酸或三烷基亚磷酸盐反应，然后将得到的铵盐进行离子交换。

  公开号：

  WO2005115969A1
• 作为产物：
  描述：

  四甲基氢氧化铵 在 磷酸 作用下， 生成 tris(tetramethylammonium) phosphate
  参考文献：
  名称：

  由四烷基铵客人精调基于阴离子的三螺旋结构的弹簧运动

  摘要：

  超分子弹簧是一类分子装置，可从分子水平上对宏观弹簧的行为产生影响。螺旋结构是合适的分子弹簧，因为螺旋线的特定扭曲会在外部刺激下引起沿轴的弹簧状（伸展-收缩）运动。在此，我们报告一个基于阴离子的三螺旋弹簧，该弹簧可以通过引入和除去四烷基铵阳离子（包括TMA +）进行可逆的伸缩运动。与类似的不规则四面体阳离子带有不同的烷基链，而两个磷酸根离子的相对方向发生变化以利于客体夹杂。值得注意的是，可以通过改变客体阳离子的形状和大小来微调收缩度（缩短螺距）。但是，使用较大的阳离子（TEA +，TPA +和TBA +），可获得中螺旋结构，可通过添加/去除TMA +离子与螺旋结构互变。

  DOI：

  10.1002/anie.202100294
• 作为试剂：
  描述：

  2-巯基乙醇 、 {(S)-2-[4-(2-Bromo-acetylamino)-benzyl]-4,7,10-tris-carboxymethyl-1,4,7,10-tetraaza-cyclododec-1-yl}-acetic acid 在 三乙胺 、 tris(tetramethylammonium) phosphate 作用下， 反应 0.33h， 生成 ((S)-4,7,10-Tris-carboxymethyl-2-{4-[2-(2-hydroxy-ethylsulfanyl)-acetylamino]-benzyl}-1,4,7,10-tetraaza-cyclododec-1-yl)-acetic acid
  参考文献：
  名称：

  Crystal Structures of Two Complexes of the Rare-Earth-DOTA-Binding Antibody 2D12.5:  Ligand Generality from a Chiral System

  摘要：

  We report the crystal structures of antibody 2D12.5 Fab bound to an yttrium-DOTA analogue and separately to a gadolinium-DOTA analogue. The rare earth elements have many useful properties as probes, and 2D12.5 binds the DOTA (1,4,7,10-tetraazacyclododecane-N,N",N",IV""-tetraacetic acid) complexes of all of them (Corneillie et al. J. Am. Chem. Soc. 2003, 125, 3436-3437). The structures show that there are no direct protein-metal interactions: a bridging water acts as a link between the protein and metal, with the chelate present as the M isomer in each case. DOTA forms an amphipathic cylinder with the charged carboxylate groups toward the face of the chelate near the metal ion, while nonpolar methylene groups from the macrocycle and the carboxymethyl groups occupy the rear and sides of the molecule. The orientation of the metal-DOTA in the 2D12.5 complex places most of the methylene carbon atoms of DOTA in hydrophobic contact with aromatic protein side chains. Other binding interactions between the metal complex and the antibody include a bidentate salt bridge, four direct H-bonds, and four to five water-mediated H-bonds. We find that 2D12.5 exhibits enantiomeric binding generality, binding yttrium chelates in both Delta(deltadeltadeltadelta) and Delta(lambdalambdalambdalambda) configurations with modestly different affinities. This develops from the symmetrical nature of the DOTA chelate, which places heteroatoms and hydrophobic atoms in approximately the same relative positions regardless of the helicity of DOTA.

  DOI：

  10.1021/ja037236y

文献信息

• Room-Temperature Copper-Catalyzed Carbon-Nitrogen Coupling of Aryl Iodides and Bromides Promoted by Organic Ionic Bases
  作者：Chu-Ting Yang、Yao Fu、Yao-Bing Huang、Jun Yi、Qing-Xiang Guo、Lei Liu

  DOI：10.1002/anie.200903158

  日期：2009.9.21

  solubility alone does not explain the performance of organic ionic bases in the room‐temperature coupling of aryl iodides and even bromides with aliphatic and aromatic amines and N‐heterocycles (NuH; see scheme). Conductivity measurements show that these organic ionic bases, which contain tetraalkylammonium or ‐phosphonium cations, are readily ionized in organic solvents.

  仅仅良好的溶解度并不能解释有机离子碱在芳基碘化物甚至溴化物与脂族和芳族胺以及N杂环的室温偶联中的性能（NuH；参见方案）。电导率测量表明，这些含有四烷基铵或阳离子的有机离子碱在有机溶剂中很容易被电离。
• Alkylation of Ammonium Salts Catalyzed by Imidazolium-Based Ionic Liquid Catalysts
  作者：Zhuo Qun Zheng、Jie Wang、Ting Hua Wu、Xiao Ping Zhou

  DOI：10.1002/adsc.200600451

  日期：2007.5.7

  Quaternary ammonium salts were synthesized from ammonium salts and dialkyl carbonates over imidazolium ionic liquid catalysts. The reaction gave almost stoichiometric amounts of the quaternary ammonium salts for halides and nitrates. It was found that the electron-donating property of the alkyl moieties of ammonium cations, the electrophilic nature of the alkyl group of the carbonate, the acidity of

  在咪唑鎓离子液体催化剂上由铵盐和碳酸二烷基酯合成季铵盐。该反应产生了几乎化学计量的用于卤化物和硝酸盐的季铵盐。发现铵阳离子的烷基部分的供电子性，碳酸盐烷基的亲电子性质，铵盐的阴离子所对应的酸的酸度以及铵的空间位阻。盐和碳酸二烷基酯是影响季铵盐收率的关键因素。铵盐氮原子上的强供电子烷基，碳酸二烷基酯的亚甲基碳上的吸电子基团，
• Chirality transcription in the anion-coordination-driven assembly of tetrahedral cages
  作者：Jin Fu、Bo Zheng、Huizheng Zhang、Yanxia Zhao、Dan Zhang、Wenyao Zhang、Xiao-Juan Yang、Biao Wu

  DOI：10.1039/c9cc09752j

  日期：——

  Enantiopure A₄L₄ tetrahedral cages were obtained through chirality transfer in the anion-coordination-driven assembly (ACDA) of chiral C₃-symmetric tris-bis(urea) ligands with phosphate.

  通过手性转移，在手性C3对称的三双(脲)配体与磷酸盐的阴离子协同驱动组装中获得了纯对映体A4L4四面体笼。
• Peripheral Templation-Modulated Interconversion between an A₄ L₆ Tetrahedral Anion Cage and A₂ L₃ Triple Helicate with Guest Capture/Release
  作者：Xuemin Bai、Chuandong Jia、Yanxia Zhao、Dong Yang、Shi-Cheng Wang、Anyang Li、Yi-Tsu Chan、Yao-Yu Wang、Xiao-Juan Yang、Biao Wu

  DOI：10.1002/anie.201712080

  日期：2018.2.12

  An anion‐coordination‐based A4L6 (“A” denotes anion and “L” is ligand) tetrahedral cage was constructed by a C2‐symmetric bis‐bis(urea) ligand and phosphate anion, which showed reversible interconversion with the A2L3 triple helicate as a response to the template, concentration, or solvent. Notably, an unusual “peripheral” templation was found to be critical to stabilize the tetrahedral structure.

  基于阴离子配位的A 4 L 6（“ A”表示阴离子，“ L”是配体）由C 2对称的双-双（脲）配体和磷酸根阴离子构成四面体笼，表明与阴离子具有可逆的相互转化。阿2大号3三重helicate为模板，浓度，或溶剂中的反应。值得注意的是，发现异常的“外围”模板对于稳定四面体结构至关重要。利用这种外围效应来组装一个“空的” A 4 L 6笼子，该笼子可以通过多种刺激控制地捕获/释放生物学上重要的物种，例如胆碱和乙酰胆碱。
• Anion-Coordination-Driven Assembly of Chiral Quadruple and Single Helices Controlled by Countercations
  作者：Boyang Li、Bo Zheng、Wenyao Zhang、Dan Zhang、Xiao-Juan Yang、Biao Wu

  DOI：10.1021/acs.cgd.9b00982

  日期：2019.11.6

  Enantiopure helical assemblies were constructed by chiral C2-symmetric bis-bis(urea) ligands (LS/R) with phosphate or hydrogen phosphate anion, which is dictated by the countercation. In the presence of smaller cations (TMA+ or TEA+), the chiral ligands coordinate to dihydrated phosphate to form homochiral quadruple helicates (TMA)6[(PO4·2H2O)2LS/R4]. However, when larger cations (TPA+ or TBA+) were used, the ligand tends to assemble with monohydrated hydrogen phosphate ions into infinite single helices (TPA)2n[(HPO4·H2O)LS/R]n or (TBA)2n[(HPO4·H2O)LS/R]n. The predisposed point chirality next to the anion binding center in the ligands has a profound impact on the resulting assemblies, and their chirality is manipulated in a predictable manner.

  手性 C2 对称双（脲）配体（LS/R）与磷酸或磷酸氢阴离子构建了对映纯螺旋组件，这是由反阳离子决定的。在较小的阳离子（TMA+ 或 TEA+）存在时，手性配体与二水磷酸配位，形成同性四螺旋体 (TMA)6[(PO4-2H2O)2LS/R4]。然而，当使用较大的阳离子（TPA+ 或 TBA+）时，配体倾向于与一水磷酸氢根离子组装成无限单螺旋体 (TPA)2n[(HPO4-H2O)LS/R]n 或 (TBA)2n[(HPO4-H2O)LS/R]n。配体中阴离子结合中心旁边的预设点手性对所产生的集合体有着深远的影响，而且它们的手性是以可预测的方式操纵的。